Unexpected nitrogen–oxygen exchange reactions in cyclic metallaphosphazenes; synthesis and X-ray crystal structures of [Mo(OPPh2NHPPh2O)O2Cl2], [Mo(OPPh2NPPh2O)2(O)Cl], and [Mo(OPPh2NPPh2O)2O2]

The reactions of [[graphic omitted])Cl3] with Ph3SiOH and ButOH lead not to the expected substitution products but to exchange and rearrangement reactions in which the nitrogen atoms which co-ordinate molybdenum are replaced by oxygen. The crystal structures of [[graphic omitted])O2Cl2], [[graphic omitted])2(O)Cl], and [graphic omitted])2O2] are reported, together with the synthesis of these unexpected products by more direct routes.

[1]  J. M. Mayer.  Metal-oxygen multiple bond lengths: a statistical study , 1988 .

[2]  K. Peters,et al.  The First “Adamantoid” Alkaline Earth Metal Chelate Complex: Synthesis, Structure, and Reactivity , 1988 .

[3]  H. Roesky,et al.  Synthese und Struktur von [ClV(OSiMe3)N2PPh2]2, dem ersten Cyclodimetallaphosphazen — ein achtgliedriger, planarer, ungesättigter Heterocyclus , 1988 .

[4]  G. Sheldrick,et al.  Synthesis and Structure of [CIV(OSiMe3)N2PPh2]2, the First Cyclodimetallaphosphazene–an Eight‐Membered Planar Unsaturated Heterocycle , 1988 .

[5]  K. Katti,et al.  A new class of inorganic heterocycles from insertion of transition metals into the cyclophosphazene skeleton - synthesis and characterization of six-membered rings with vanadium, tungsten, and rhenium in high oxidation states , 1987 .

[6]  H. Roesky,et al.  Synthese und Struktur des ersten Cyclophosphazens mit einer Metall—Metall-Bindung im Ringgerüst / Synthesis and Structure of the First Cyclophosphazene Containing a Metal —Metal Bond within the Ring Skeleton , 1987 .

[7]  G. Sheldrick,et al.  New heterocyclic compounds containing niobium and molybdenum; crystal structure of a cyclomolybdaphosphazene , 1987 .

[8]  K. Barnhart,et al.  Syntheses, structures, and spectroscopic properties of six-coordinate mononuclear oxo-molybdenum(V) complexes stabilized by the hydrotris(3,5-dimethyl-1-pyrazolyl)borate ligand , 1987 .

[9]  K. Katti,et al.  Synthesis and characterization of new heterocyclic compounds of tungsten, selenium, and tellurium , 1987 .

[10]  G. M. Sheldrick,et al.  Ein Übergangsmetallatom als Baustein eines cyclischen Phosphazens — Synthese und Struktur von [Cl3WN3(PPh2)2] , 1986 .

[11]  G. Sheldrick,et al.  A Transition Metal Atom as Building Block of a Cyclic Phosphazene– Synthesis and Structure of [Cl3WN3(PPh2)2] , 1986 .

[12]  D. Rogers,et al.  On the application of Hamilton's ratio test to the assignment of absolute configuration and an alternative test , 1981 .

[13]  W. A. Nugent,et al.  Some bis(tert-butylimido) complexes of the Group 6 transition metals and a related alkylamido derivative , 1980 .

[14]  N. Rodier,et al.  Structure d'une deuxième variété cristalline du dioxodichlorobis(hexaméthylphosphoramide)molybdène(VI) , 1977 .

[15]  N. Rodier,et al.  Structure cristalline du dioxodichlorobis(hexaméthylphosphoramide)molybdène(VI) , 1977 .

[16]  A. Schmidpeter,et al.  EPR-Spektren von Imidodiphosphinatokupfer(II)-Chelaten , 1967 .

[17]  A. Schmidpeter,et al.  Imidodiphosphinato‐Metallchelate, Neutralkomplexe mit kohlenstoff‐freiem Chelatring , 1964 .

[18]  A. Schmidpeter,et al.  Imidodiphosphinatometal Chelates, Neutral Complexes with Carbon‐Free Chelate Rings , 1964 .

[19]  E. Fluck,et al.  Zur Kenntnis der Imido‐diphosphonsäuren und ihrer Derivate, II. Imido‐tetraphenyl‐diphosphinsäure und ihr Trichlorid , 1963 .

[20]  N. Platzer,et al.  Lanthanide tetraphenylimidodiphosphinates: X-ray structure of an ethyl acetate adduct and use as n.m.r. shift reagents for acids , 1987 .

[21]  J. Atwood,et al.  Siloxy-zirconium chemistry. 1. Reaction of zirconium-carbon .sigma.-bonds with R3SiOH and the crystal structure of (1,2-dimethoxyethane)bis(triphenylsiloxy)dichlorozirconium(IV), (DME)ZrCl2(OSiPh3)2 , 1986 .

[22]  M. Chisholm,et al.  Reactions involving the triple bond in dimolybdenum and ditungsten hexa-alkoxides and C–C, C–N, and C–O triple bonds , 1985 .

[23]  W. Clegg.  Faster data collection without loss of precision. An extension of the learnt profile method , 1981 .